TY - JOUR
T1 - Template-Mediated Control over Polymorphism in the Vapor-Assisted Formation of Zeolitic Imidazolate Framework Powders and Films
AU - Tu, Min
AU - Kravchenko, Dmitry E.
AU - Xia, Benzheng
AU - Rubio-Giménez, Víctor
AU - Wauteraerts, Nathalie
AU - Verbeke, Rhea
AU - Vankelecom, Ivo F.J.
AU - Stassin, Timothée
AU - Egger, Werner
AU - Dickmann, Marcel
AU - Amenitsch, Heinz
AU - Ameloot, Rob
N1 - Funding Information:
R.A. acknowledges funding from the European Research Council (No. 716472, VAPORE), the Research Foundation Flanders (FWO) for funding in the research projects G083016N, G0E639N, and 1501618 N and the infrastructure project G0H0716N, and KU Leuven for funding in the research project C32/18/056. This research project has received funding from the EU's H2020 framework program for research and innovation under grant agreements 801464 FETOPEN-1?2016-2017 and 654360 NFFA-Europe (proposal IDs 462, 596, and 854). V.R.-G. acknowledges FWO for a Marie Sk?odowska Curie Actions?Seal of Excellence Postdoctoral Fellowship (196025/12Z6520N). D.K. acknowledges the Marie Sklodowska Curie Training Network HYCOAT (No. 765378) for the financial support. R.V. and T.S. thank FWO for PhD fellowships (1S00917N and 1S53316N, respectively).
Funding Information:
R.A. acknowledges funding from the European Research Council (No. 716472, VAPORE), the Research Foundation Flanders (FWO) for funding in the research projects G083016N, G0E639N, and 1501618 N and the infrastructure project G0H0716N, and KU Leuven for funding in the research project C32/18/056. This research project has received funding from the EU's H2020 framework program for research and innovation under grant agreements 801464 FETOPEN‐1–2016‐2017 and 654360 NFFA‐Europe (proposal IDs 462, 596, and 854). V.R.‐G. acknowledges FWO for a Marie Skłodowska Curie Actions—Seal of Excellence Postdoctoral Fellowship (196025/12Z6520N). D.K. acknowledges the Marie Sklodowska Curie Training Network HYCOAT (No. 765378) for the financial support. R.V. and T.S. thank FWO for PhD fellowships (1S00917N and 1S53316N, respectively).
Publisher Copyright:
© 2020 Wiley-VCH GmbH
PY - 2021/3/29
Y1 - 2021/3/29
N2 - The landscape of possible polymorphs for some metal–organic frameworks (MOFs) can pose a challenge for controlling the outcome of their syntheses. Demonstrated here is the use of a template to control in the vapor-assisted formation of zeolitic imidazolate framework (ZIF) powders and thin films. Introducing a small amount of either ethanol or dimethylformamide vapor during the reaction between ZnO and 4,5-dichloroimidazole vapor results in the formation of the porous ZIF-71 phase, whereas other conditions lead to the formation of the dense ZIF-72 phase or amorphous materials. Time-resolved in situ small-angle X-ray scattering reveals that the porous phase is metastable and can be transformed into its dense polymorph. This transformation is avoided through the introduction of template vapor. The porosity of the resulting ZIF powders and films was studied by N2 and Kr physisorption, as well as positron annihilation lifetime spectroscopy. The templating principle was demonstrated for other members of the ZIF family as well, including the ZIF-7 series, ZIF-8_Cl, and ZIF-8_Br.
AB - The landscape of possible polymorphs for some metal–organic frameworks (MOFs) can pose a challenge for controlling the outcome of their syntheses. Demonstrated here is the use of a template to control in the vapor-assisted formation of zeolitic imidazolate framework (ZIF) powders and thin films. Introducing a small amount of either ethanol or dimethylformamide vapor during the reaction between ZnO and 4,5-dichloroimidazole vapor results in the formation of the porous ZIF-71 phase, whereas other conditions lead to the formation of the dense ZIF-72 phase or amorphous materials. Time-resolved in situ small-angle X-ray scattering reveals that the porous phase is metastable and can be transformed into its dense polymorph. This transformation is avoided through the introduction of template vapor. The porosity of the resulting ZIF powders and films was studied by N2 and Kr physisorption, as well as positron annihilation lifetime spectroscopy. The templating principle was demonstrated for other members of the ZIF family as well, including the ZIF-7 series, ZIF-8_Cl, and ZIF-8_Br.
KW - chemical vapor deposition
KW - metal–organic frameworks
KW - physiosorption
KW - template synthesis
KW - thin films
UR - http://www.scopus.com/inward/record.url?scp=85101607959&partnerID=8YFLogxK
U2 - 10.1002/anie.202014791
DO - 10.1002/anie.202014791
M3 - Article
C2 - 33350565
AN - SCOPUS:85101607959
SN - 1433-7851
VL - 60
SP - 7553
EP - 7558
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 14
ER -